US4270944A - Method for producing calcium borates - Google Patents
Method for producing calcium borates Download PDFInfo
- Publication number
- US4270944A US4270944A US06/111,437 US11143780A US4270944A US 4270944 A US4270944 A US 4270944A US 11143780 A US11143780 A US 11143780A US 4270944 A US4270944 A US 4270944A
- Authority
- US
- United States
- Prior art keywords
- calcium
- ulexite
- sub
- solution
- precipitate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/12—Borates
- C01B35/126—Borates of alkaline-earth metals, beryllium, aluminium or magnesium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
Definitions
- This invention relates to a process for producing calcium borates having particularly useful properties.
- these properties are a relatively high percentage of B 2 O 3 , a relatively low percentage or complete absence of Na 2 O and an unusually low water content.
- B 2 O 3 may be supplied by many different borate compounds. The following is a list of some of the more readily available borate compounds:
- calcium borates are precipitated from an aqueous ulexite solution.
- the ulexite is dissolved in a mineral acid such as hydrochloric acid.
- Calcium chloride brine is then added and the pH is adjusted to precipitate hydrated calcium borates. pH adjustment can be carried out by the addition of sodium hydroxide.
- the precipitate can be dried if less hydrated calcium borates are desired.
- the calcium borates so produced have properties similar to colemanite and calcined colemanite.
- Calcium fluoride is very insoluble in water and would not be included.
- Other halide salts which are included are those of aluminum, magnesium, barium and the like.
- Mineral acids other than hydrochloric acid can be employed in this invention.
- Other common mineral acids include sulfuric acid, nitric acid and the like.
- the concentration of mineral acid employed in this invention can vary widely. Generally, however, the mineral acid has a concentration ranging from 0.2 to 3.0 M, preferably 0.3 to 2.0 M.
- the mole ratio of calcium chloride and ulexite employed in this invention also can vary widely. Generally, however, the calcium chloride calculated as Ca and the ulexite calculated as B are present in initial amounts having a molar ratio of Ca/B ranging from 0.1 to 1.0, preferably 0.1 to 0.4.
- the concentration of calcium chloride and ulexite can vary widely. Generally, an amount necessary to dissolve in solution and meet the above mole ratio is required. Otherwise the concentration of each material can be as weak or as strong as desired.
- the properties of compacted glass batch produced from these calcium borates would compare favorably with those compacted from standard glass batches.
- the calcium borate In order to be useful for glass batch compacting, the calcium borate must first be dried at about 100° C. for an hour to remove loosely bound water. The small amount of remaining water will not be expected to affect the compacting process.
- the ulexite used in these experiments was Boratos Del Peru ulexite. Analysis showed the ulexite to have the oxide composition 6.9%, Na 2 O, 9.9% CaO, and 41.8% B 2 O 3 .
- Table 1 shows the compositions of the calcium borates which were produced. Sodium, boron, calcium, and chlorine were analyzed by the procedures described by the following Examples. The percent of water was determined from the weight loss after heating the sample to 500° C. for one hour.
- the first number in Table 1 is the molar ratio of the calcium which was added as calcium chloride to the boron present in the ulexite. These three ratios are approximately that necessary for replacing every 2 moles of sodium in the ulexite with 1 mole of calcium from the calcium chloride solution, for replacing 1 mole of sodium with 1 mole of calcium, and for replacing 1 mole of sodium with 2 moles of calcium, respectively. Although different amounts of calcium were added to the ulexite, only one calcium borate was produced. Its x-ray diffraction pattern shows it to be amorphous. The most likely composition for it is 3CaO.5B 2 O 3 .2H 2 O.
- the yield of the product is dependent on the pH of the solution as is shown in Table 2. Adjusting the pH is one way this process might be optimized.
- the buffer solution mentioned here is prepared by dissolving about 7 grams of NH 4 Cl in 60 ml of concentrated NH 4 OH solution and diluting it in 100 ml of distilled water.
- the EDTA solution is made by dissolving 18 grams of the disodium salt of ethylenediaminetetraacetic acid in somewhat less than 1000 ml of distilled water. Then 0.3 grams of MgCl 2 .6H 2 O are dissolved in it and the solution is made up to 1000 ml ml.
- the EDTA solution is standardized by dissolving accurately weighted 0.2 gram samples of dry CaCO 3 in a small amount of HCl solution. They are then titrated with the EDTA solution following the above procedure starting at step (2).
- the 0.1 M HCl and NaOH are conveniently standardized by titrating an accurately weighed sample of dry Na 2 CO 3 with the HCl and then by titrating the NaOH with the HCl using a pH meter.
- One mole of the AgCl precipitate is equivalent to one mole of Cl in the sample.
- Betaprobe an electron excited X-ray fluorescence spectrometer
- the intensity of the sodium peak as a function of sodium concentration for the standards was fit to a straight line and the concentration of sodium in the unknown was interplated from this.
- agglomerates are composite, integral, self-supporting masses consisting essentially of all the substantial batch materials and may take the form of balls, extrusions, discs, briquettes, and pellets.
- the pellets are discharged to a vertical bed contained within a chamber and furnace flue gases pass, in direct contact with and countercurrently to, downwardly moving pellets of the bed to dry and preheat them.
- the process is carried out at a temperature and for a time insufficient to fuse or melt substantial amounts of the agglomerates.
- the agglomerates usually will start to fuse together when their temperature reaches 1,400° or 1,500° F., so contact is discontinued at or below these temperatures.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Glass Compositions (AREA)
- Paper (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/111,437 US4270944A (en) | 1980-01-11 | 1980-01-11 | Method for producing calcium borates |
BE0/203090A BE886555A (fr) | 1980-01-11 | 1980-12-09 | Procede de fabrication de borates de calcium |
FR8026235A FR2473491A1 (fr) | 1980-01-11 | 1980-12-10 | Procede de fabrication de borates de calcium |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/111,437 US4270944A (en) | 1980-01-11 | 1980-01-11 | Method for producing calcium borates |
Publications (1)
Publication Number | Publication Date |
---|---|
US4270944A true US4270944A (en) | 1981-06-02 |
Family
ID=22338546
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/111,437 Expired - Lifetime US4270944A (en) | 1980-01-11 | 1980-01-11 | Method for producing calcium borates |
Country Status (3)
Country | Link |
---|---|
US (1) | US4270944A (ro) |
BE (1) | BE886555A (ro) |
FR (1) | FR2473491A1 (ro) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4475771A (en) * | 1983-03-28 | 1984-10-09 | Duval Corporation | Cyclic solution mining of borate ores |
US4952358A (en) * | 1986-09-05 | 1990-08-28 | Inoue Mtp Kabushiki Kaisha | Method of manufacturing an interior member for vehicles |
EP0460568A2 (en) * | 1990-06-08 | 1991-12-11 | Colorobbia Italia S.p.a. | Process for disaggregating boronatrocalcite ore in an alkaline medium for the production of sodium borate and calcium borate |
EP0571047A1 (en) * | 1992-05-22 | 1993-11-24 | Bormine S.A. | Process for the preparation of precipitated borates |
US5268154A (en) * | 1990-06-08 | 1993-12-07 | Bitossi Dianella S.P.A. | Process for disaggregating boronatrocalcite ore in an alkaline medium for the production of sodium borate and calcium borate |
FR2750413A1 (fr) * | 1996-06-28 | 1998-01-02 | Materias Primas Magdalena S A | Procede d'obtention de borate de calcium purifie et produit obtenu |
US5869014A (en) * | 1995-03-01 | 1999-02-09 | Carranza; Manuel Camarena | Process for the production of purified, synthetic calcium borate |
CN1099375C (zh) * | 1996-07-11 | 2003-01-22 | 麦特里斯-普莱麦斯-玛格达伦纳公司 | 生产纯化的合成硼酸钙的方法 |
CN1321888C (zh) * | 2005-01-10 | 2007-06-20 | 大石桥市硼制品厂 | 用钠硼解石制造硼酸钙的方法 |
WO2012079185A1 (es) * | 2010-12-17 | 2012-06-21 | Iholdi Minerales De Atacama Ltda | Proceso de obtención de boro a partir de salmueras naturales o industriales y/o minerales que comprenden boro, utilizando un extractante inorgánico para extraer el boro. |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1185216A (en) * | 1913-12-24 | 1916-05-30 | Roessler & Hasslacher Chemical | Compounds containing active oxygen. |
US1200739A (en) * | 1913-12-24 | 1916-10-10 | Roessler & Hasslacher Chemical | Compound containing active oxygen and the process of making the same. |
GB352137A (en) * | 1930-04-28 | 1931-07-09 | Henry Blumenberg Jr | Treatment of borax ores |
US2867502A (en) * | 1954-08-16 | 1959-01-06 | Olin Mathieson | Production of ammonium pentaborate and boric oxide from borax |
US3026178A (en) * | 1958-10-16 | 1962-03-20 | Callery Chemical Co | Preparation of boric oxide and boric acid |
US3032392A (en) * | 1958-10-29 | 1962-05-01 | United States Borax Chem | Manufacture of calcium borates |
US3032391A (en) * | 1958-08-20 | 1962-05-01 | United States Borax Chem | Production of calcium borates |
US3088801A (en) * | 1961-06-22 | 1963-05-07 | Du Pont | Chromium and boron containing product and process for producing same |
US3450497A (en) * | 1966-07-05 | 1969-06-17 | American Potash & Chem Corp | Process for producing boric oxide |
US4074991A (en) * | 1976-11-08 | 1978-02-21 | Ppg Industries, Inc. | Method of preparing boric acid-containing glass batch |
-
1980
- 1980-01-11 US US06/111,437 patent/US4270944A/en not_active Expired - Lifetime
- 1980-12-09 BE BE0/203090A patent/BE886555A/fr not_active IP Right Cessation
- 1980-12-10 FR FR8026235A patent/FR2473491A1/fr active Granted
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1185216A (en) * | 1913-12-24 | 1916-05-30 | Roessler & Hasslacher Chemical | Compounds containing active oxygen. |
US1200739A (en) * | 1913-12-24 | 1916-10-10 | Roessler & Hasslacher Chemical | Compound containing active oxygen and the process of making the same. |
GB352137A (en) * | 1930-04-28 | 1931-07-09 | Henry Blumenberg Jr | Treatment of borax ores |
US2867502A (en) * | 1954-08-16 | 1959-01-06 | Olin Mathieson | Production of ammonium pentaborate and boric oxide from borax |
US3032391A (en) * | 1958-08-20 | 1962-05-01 | United States Borax Chem | Production of calcium borates |
US3026178A (en) * | 1958-10-16 | 1962-03-20 | Callery Chemical Co | Preparation of boric oxide and boric acid |
US3032392A (en) * | 1958-10-29 | 1962-05-01 | United States Borax Chem | Manufacture of calcium borates |
US3088801A (en) * | 1961-06-22 | 1963-05-07 | Du Pont | Chromium and boron containing product and process for producing same |
US3450497A (en) * | 1966-07-05 | 1969-06-17 | American Potash & Chem Corp | Process for producing boric oxide |
US4074991A (en) * | 1976-11-08 | 1978-02-21 | Ppg Industries, Inc. | Method of preparing boric acid-containing glass batch |
Non-Patent Citations (2)
Title |
---|
"Boron, Metallo-Boron Compounds & Boranes," by R. M. Adams Manual of Mineralogy, -Dana, pp. 64, 65. * |
"Kirk-Othmer Encyclopedia of Chemical Tech.," vol. 3, 2nd revised edition, p. 649. * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4475771A (en) * | 1983-03-28 | 1984-10-09 | Duval Corporation | Cyclic solution mining of borate ores |
US4952358A (en) * | 1986-09-05 | 1990-08-28 | Inoue Mtp Kabushiki Kaisha | Method of manufacturing an interior member for vehicles |
EP0460568A2 (en) * | 1990-06-08 | 1991-12-11 | Colorobbia Italia S.p.a. | Process for disaggregating boronatrocalcite ore in an alkaline medium for the production of sodium borate and calcium borate |
EP0460568A3 (en) * | 1990-06-08 | 1992-10-14 | Bitossi Dianella S.P.A. | Process for disaggregating boronatrocalcite ore in an alkaline medium for the production of sodium borate and calcium borate |
US5268154A (en) * | 1990-06-08 | 1993-12-07 | Bitossi Dianella S.P.A. | Process for disaggregating boronatrocalcite ore in an alkaline medium for the production of sodium borate and calcium borate |
TR26278A (tr) * | 1990-06-08 | 1995-02-15 | Bitossi Dianella Spa | SODYUM BORAT VE KALSIYUM BORATIN üRETIMI ICIN BIR ALKALIN ORTAM ICINDE BORONATROKALSIT CEVHERI- NIN DAGINIK TUTULMASI ICIN ISLEM |
EP0571047A1 (en) * | 1992-05-22 | 1993-11-24 | Bormine S.A. | Process for the preparation of precipitated borates |
US5869014A (en) * | 1995-03-01 | 1999-02-09 | Carranza; Manuel Camarena | Process for the production of purified, synthetic calcium borate |
FR2750413A1 (fr) * | 1996-06-28 | 1998-01-02 | Materias Primas Magdalena S A | Procede d'obtention de borate de calcium purifie et produit obtenu |
CN1099375C (zh) * | 1996-07-11 | 2003-01-22 | 麦特里斯-普莱麦斯-玛格达伦纳公司 | 生产纯化的合成硼酸钙的方法 |
CN1321888C (zh) * | 2005-01-10 | 2007-06-20 | 大石桥市硼制品厂 | 用钠硼解石制造硼酸钙的方法 |
WO2012079185A1 (es) * | 2010-12-17 | 2012-06-21 | Iholdi Minerales De Atacama Ltda | Proceso de obtención de boro a partir de salmueras naturales o industriales y/o minerales que comprenden boro, utilizando un extractante inorgánico para extraer el boro. |
Also Published As
Publication number | Publication date |
---|---|
BE886555A (fr) | 1981-06-09 |
FR2473491A1 (fr) | 1981-07-17 |
FR2473491B3 (ro) | 1983-10-14 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: OWENS-CORNING FIBERGLAS CORPORATION A CORP. OF, DE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:EASTES WALTER L.;TARANTINO ANNA;REEL/FRAME:003810/0415 Effective date: 19800104 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
AS | Assignment |
Owner name: WILMINGTON TRUST COMPANY, ONE RODNEY SQUARE NORTH, Free format text: SECURITY INTEREST;ASSIGNOR:OWENS-CORNING FIBERGLAS CORPORATION;REEL/FRAME:004652/0351 Effective date: 19861103 Owner name: WADE, WILLIAM, J., ONE RODNEY SQUARE NORTH, WILMIN Free format text: SECURITY INTEREST;ASSIGNOR:OWENS-CORNING FIBERGLAS CORPORATION;REEL/FRAME:004652/0351 Effective date: 19861103 Owner name: WILMINGTON TRUST COMPANY, DELAWARE Free format text: SECURITY INTEREST;ASSIGNOR:OWENS-CORNING FIBERGLAS CORPORATION;REEL/FRAME:004652/0351 Effective date: 19861103 Owner name: WADE, WILLIAM, J., DELAWARE Free format text: SECURITY INTEREST;ASSIGNOR:OWENS-CORNING FIBERGLAS CORPORATION;REEL/FRAME:004652/0351 Effective date: 19861103 |
|
AS | Assignment |
Owner name: OWENS-CORNING FIBERGLAS CORPORATION, FIBERGLAS TOW Free format text: TERMINATION OF SECURITY AGREEMENT RECORDED NOV. 13, 1986. REEL 4652 FRAMES 351-420;ASSIGNORS:WILMINGTON TRUST COMPANY, A DE. BANKING CORPORATION;WADE, WILLIAM J. (TRUSTEES);REEL/FRAME:004903/0501 Effective date: 19870730 Owner name: OWENS-CORNING FIBERGLAS CORPORATION, A CORP. OF DE Free format text: TERMINATION OF SECURITY AGREEMENT RECORDED NOV. 13, 1986. REEL 4652 FRAMES 351-420;ASSIGNORS:WILMINGTON TRUST COMPANY, A DE. BANKING CORPORATION;WADE, WILLIAM J. (TRUSTEES);REEL/FRAME:004903/0501 Effective date: 19870730 |
|
AS | Assignment |
Owner name: OWENS-CORNING FIBERGLAS TECHNOLOGY INC., ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:OWENS-CORNING FIBERGLAS CORPORATION, A CORP. OF DE;REEL/FRAME:006041/0175 Effective date: 19911205 |